CN105470002A - Preparation method of nickel cobaltite porous micron belt/foamed nickel composite electrode material - Google Patents
Preparation method of nickel cobaltite porous micron belt/foamed nickel composite electrode material Download PDFInfo
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- CN105470002A CN105470002A CN201510848187.5A CN201510848187A CN105470002A CN 105470002 A CN105470002 A CN 105470002A CN 201510848187 A CN201510848187 A CN 201510848187A CN 105470002 A CN105470002 A CN 105470002A
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- nickel foam
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 248
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 124
- 239000007772 electrode material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title abstract description 4
- 229910052963 cobaltite Inorganic materials 0.000 title abstract 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000011148 porous material Substances 0.000 claims abstract description 41
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 150000002815 nickel Chemical class 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 59
- 239000010941 cobalt Substances 0.000 claims description 59
- 239000006260 foam Substances 0.000 claims description 59
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 58
- 239000002253 acid Substances 0.000 claims description 52
- 238000010438 heat treatment Methods 0.000 claims description 12
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 11
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- 229910052755 nonmetal Inorganic materials 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the inorganic non-metal material preparation field and relates to a preparation method of a nickel cobaltite porous micron belt/foamed nickel composite electrode material. The preparation method includes the following steps that: clean foamed nickel is immersed in an oxalic acid aqueous solution; a soluble nickel salt and soluble cobalt salt mixed aqueous solution is added in an obtained solution dropwise under stirring at room temperature; stirring is performed until a micron structure precursor grows from the surface of the foamed nickel through a reaction; the foamed nickel is removed out, and cleaning, drying and calcining are performed sequentially, so that the nickel cobaltite porous micron belt/foamed nickel composite electrode material can be obtained. The preparation method of the invention has the advantages of simple and feasible process, high product purity and low production cost. With the method adopted, an obtained product has a novel appearance, and is firmly grown on the surface of the high-conductivity foamed nickel; the thickness of the nickel cobaltite porous micron belt ranges from 50 to 80 nm, and the length of the nickel cobaltite porous micron belt ranges from 3 to 5 microns, and the width of the nickel cobaltite porous micron belt ranges from 300 to 500 microns, and the size of a nano pore ranges from 5 to 20nm; and the homogeneity and dispersity of the product are excellent.
Description
Technical field
The invention belongs to the preparing technical field of Inorganic Non-metallic Materials, specifically relate to the preparation method of a kind of cobalt acid nickel multi-pore micron band/nickel foam combination electrode material.
Background technology
Ultracapacitor has the advantages such as power density is high, the charging interval is short, long service life, good stability and is widely used in electric automobile, and military, the fields such as mobile communication equipment, cause the extensive concern of researcher recently.Ultracapacitor can be divided into electrochemical capacitor in double electrode layer and Faraday pseudo-capacitance device principle.Common material with carbon element has that high-specific surface area, cost are low, the advantage such as to have extended cycle life and be applied in electrochemical capacitor in double electrode layer, but the low business development seriously limiting carbon-based electrode material of its ratio capacitance; Bimetallic oxide, owing to having high ratio capacitance and excellent cyclic reversibility, is therefore considered to optimal Faraday pseudo-capacitance device electrode material.In bimetallic oxide, cobalt acid nickel (NiCo
2o
4) owing to having environmental friendliness, low cost, controlled surface and structural behaviour, the most important thing is, cobalt acid nickel has very high theoretical ratio capacitance (2690F/g), and these advantages make cobalt acid nickel become a kind of ideal electrode material that can meet practical application (see KrishnanSG, ReddyMV, HarilalM, etal.CharacterizationofMgCo
2o
4asanelectrodeforhighperformancesupercapacitors [J] .ElectrochimicaActa, 2015,161:312-321).
But the actual ratio capacitance that obtains is far below theoretical value, the conductivity that this may be weak with cobalt acid nickel is relevant with low electron transfer rate.At present, there is a lot of diverse ways can improve the conductivity of cobalt acid nickel electrode material, the most effectively use the material with carbon element with excellent conductivity and uniform physical and chemical performance and cobalt acid nickel compound in these methods, such as Graphene and carbon nano-tube.But these methods all effectively can not improve the conductivity of cobalt acid nickel electrode material, therefore develop a kind of effective method raising cobalt acid nickel electrode material conductivity and remain a kind of challenge.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art part and provides a kind of technique simple, and preparation cost is low, and object product yield is high, and product purity is high, has the preparation method of the cobalt acid nickel multi-pore micron band/nickel foam combination electrode material of better chemical property.
For achieving the above object, the present invention realizes like this.
A preparation method for cobalt acid nickel multi-pore micron band/nickel foam combination electrode material is be immersed in oxalic acid aqueous solution by the nickel foam of cleaning, under the condition stirred, drips soluble nickel salt and soluble cobalt mixed aqueous solution in room temperature in above-mentioned solution; Stirring reaction, until nickel foam surface-borne goes out micrometer structure presoma, takes out nickel foam, namely obtains object product after cleaning successively, drying and calcining.
As a kind of preferred version, the molar concentration of oxalic acid aqueous solution of the present invention is 0.1 ~ 2.0mol/L; Described room temperature is at 20 ~ 30 DEG C; Described mixing speed remains on 100 ~ 150 revs/min; The speed of described dropping solution is 60 ~ 180 droplets/minute; The described stirring reaction time is 10 ~ 30 minutes.
As another kind of preferred version, soluble nickel salt of the present invention is one or its mixture of nickel nitrate or nickel chloride, and its molar concentration is 0.05 ~ 0.5mol/L; Described soluble cobalt is one or its mixture of cobalt nitrate or cobalt chloride, and its molar concentration is 0.1 ~ 1.0mol/L; The mol ratio of nickel salt and cobalt salt remains 1:2.The mol ratio of nickel salt and oxalic acid is 1:6 ~ 60.
Further, drying time of the present invention is 1 ~ 3 hour, and baking temperature is 60 ~ 120 DEG C, and heating rate is 2 ~ 10 DEG C/min.
Further, calcination time of the present invention is 2 ~ 5 hours, and calcining heat is 300 ~ 450 DEG C, and heating rate is 2 ~ 20 DEG C/min.
The present invention adopts at conductive substrates surface in situ growing metal oxide electrode material, the diffusion mass transfer performance that effectively can improve active material conductivity, increase operation rate, increase active surface, improve material.Utilize co-precipitation-calcining two-step method, successfully prepare cobalt acid nickel multi-pore micron band/nickel foam combination electrode material.Due to the existence of porous nano linear array structure, make material have larger specific area and abundant space, these structures are conducive to the transmission of electrolytical infiltration and electronics.This cobalt acid nickel multi-pore micron band/nickel foam combination electrode shows excellent electrochemical properties, is the very potential super capacitance electrode material of one.The structure of the character of this excellence and cobalt acid nickel multi-pore micron band/this novelty of nickel foam has close relationship.
Compared with prior art, the present invention has following features.
(1) present invention process route is simple, and preparation cost is low, easy to control, has higher production efficiency, and by the effective control to synthesis condition, the cobalt acid nickel micro belt of synthesis has the pore passage structure of Nano grade, adds the active sites of fake capacitance reaction.Cobalt acid nickel micron firmly grows the nickel foam metal surface in high conductivity, adds conductivity of composite material energy.
(2) the present invention prepares object product cobalt acid nickel multi-pore micron band/nickel foam combination electrode material, and its purity high (99.90% ~ 99.98%), impurity content is low, good dispersion (can be found out by SEM figure).The thickness of cobalt acid nickel multi-pore micron band is between 50 ~ 80nm, and length is at about 3 ~ 5 μm, and width is at about 300 ~ 500 μm, and nano pore size is between 5 ~ 20nm.
(3) cobalt acid nickel multi-pore micron band/nickel foam combination electrode material, can directly as electrode of super capacitor, and its ratio capacitance is high, good cycle, and the performance of this excellence and cobalt acid nickel porous nano linear array structure have close relationship.The requirement of industrial application to cobalt acid nickel loose structure electrode material product can be met.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the invention will be further described.Protection scope of the present invention is not only confined to the statement of following content.
The X-ray diffraction pattern figure of the cobalt acid nickel multi-pore micron band/nickel foam combination electrode material of Fig. 1 prepared by the present invention.
The EDX spectrogram of the cobalt acid nickel multi-pore micron band/nickel foam combination electrode material of Fig. 2 prepared by the present invention.
The SEM shape appearance figure of the cobalt acid nickel multi-pore micron band/nickel foam combination electrode material of Fig. 3 prepared by the present invention.
The SEM shape appearance figure of the cobalt acid nickel multi-pore micron band/nickel foam combination electrode material of Fig. 4 prepared by the present invention.
The SEM shape appearance figure of the cobalt acid nickel multi-pore micron band/nickel foam combination electrode material of Fig. 5 prepared by the present invention.
The SEM shape appearance figure of the cobalt acid nickel multi-pore micron band/nickel foam combination electrode material of Fig. 6 prepared by the present invention.
The SEM shape appearance figure of the cobalt acid nickel multi-pore micron band/nickel foam combination electrode material of Fig. 7 prepared by the present invention.
The SEM shape appearance figure of the cobalt acid nickel multi-pore micron band/nickel foam combination electrode material of Fig. 8 prepared by the present invention.
Embodiment
The nickel foam of cleaning is immersed in oxalic acid aqueous solution, under the condition stirred, drips the mixed aqueous solution of soluble nickel salt and soluble cobalt in room temperature to above-mentioned solution.Stirring reaction, until nickel foam surface-borne goes out micrometer structure presoma, takes out nickel foam.Cleaning successively, dry (drying time is 1 ~ 3 hour, and temperature is 60 ~ 120 DEG C, and heating rate is 2 ~ 10 DEG C/min).Namely object product (calcination time is 2 ~ 5 hours, and temperature is 300 ~ 450 DEG C, and heating rate is 2 ~ 20 DEG C/min) is obtained after calcining cooling.
Its preparation process is.
(1) nickel foam of cleaning is immersed in oxalic acid aqueous solution.
(2) under the condition stirred, the mixed aqueous solution of soluble nickel salt and soluble cobalt is dripped in room temperature to above-mentioned solution.
(3) stirring reaction is until nickel foam surface-borne goes out micrometer structure presoma, and take out nickel foam, put into baking oven after washing, programmed rate is 2 ~ 10 DEG C/min, under 60 ~ 120 DEG C of conditions, and dry 1 ~ 3 hour.
(4) above-mentioned dried after, obtained product is directly calcined in Muffle furnace, Muffle furnace Program heat up heating rate scope at 2 ~ 20 DEG C/min.Calcination time is 2 ~ 5 hours, and calcining heat is 300 ~ 450 DEG C.Naturally cobalt acid nickel porous micro-band/nickel foam combination electrode material is namely obtained after cooling.
The X-ray diffraction pattern figure (sample scrapes off measurement from nickel foam surface) of the cobalt acid nickel multi-pore micron band of Fig. 1 prepared by the present invention.
The EDX spectrogram of the cobalt acid nickel multi-pore micron band of Fig. 2 prepared by the present invention.Consequently, products obtained therefrom cobalt acid nickel loose structure electrode material is made up of nickel, cobalt and oxygen three kinds of elements.
Shown in Fig. 3 ~ 8, ESEM (SEM) figure of the cobalt acid nickel multi-pore micron band/nickel foam combination electrode material prepared by the present invention, consequently, products obtained therefrom cobalt acid nickel loose structure electrode material is micro belt pattern, and uniform growth is surperficial in the nickel foam that conductivity is high.The thickness of cobalt acid nickel multi-pore micron band is between 50 ~ 80nm, and length is at about 3 ~ 5 μm, and width is at about 300 ~ 500 μm, and nano pore size is between 5 ~ 20nm, and the dispersiveness of product and homogeneity are all fine.
Embodiment 1.
The nickel foam of cleaning is immersed in the oxalic acid aqueous solution of 1.0mol/L, it is 25 DEG C in temperature, mixing speed is under the condition of 100 revs/min, the mixed aqueous solution of nickel nitrate and cobalt nitrate is dripped in oxalic acid aqueous solution, wherein nickel nitrate molar concentration is 0.25mol/L, wherein cobalt nitrate molar concentration is 0.5mol/L, and rate of addition is 120 droplets/minute, and the mol ratio of final nickel nitrate and oxalic acid is 1:30.The stirring reaction time is 10 minutes.After reaction terminates, after nickel foam is taken out washing, put into baking oven, programmed rate 5 DEG C/min, drying 2 hours under 100 DEG C of conditions.Then be placed in Muffle furnace and calcine, calcination time is 2.5 hours, and calcining heat is 350 DEG C, and heating rate is 10 DEG C/min.Naturally cobalt acid nickel multi-pore micron crystal whisker array/nickel foam combination electrode material is namely obtained after cooling.
In mass percentage, product purity is not less than 99.96%, impurity content: carbon is less than 0.02%; Nitrogen is less than 0.02%.Using prepared cobalt acid nickel multi-pore micron crystal whisker array/nickel foam combination electrode material directly as work electrode.Under three-electrode system, test constant current charge-discharge performance, when current density is 5A/g, its ratio capacitance value is up to 692F/g.The ratio capacitance value after 3000 times that circulates only has decayed 3.5%.
Embodiment 2.
The nickel foam of cleaning is immersed in the oxalic acid aqueous solution of 1.5mol/L, it is 25 DEG C in temperature, mixing speed is under the condition of 100 revs/min, the mixed aqueous solution of nickel nitrate and cobalt nitrate is dripped in oxalic acid aqueous solution, wherein nickel nitrate molar concentration is 0.25mol/L, wherein cobalt nitrate molar concentration is 0.5mol/L, and rate of addition is 120 droplets/minute, and the mol ratio of final nickel nitrate and oxalic acid is 1:10.The stirring reaction time is 15 minutes.After reaction terminates, after nickel foam is taken out washing, put into baking oven, programmed rate 5 DEG C/min, drying 2 hours under 100 DEG C of conditions.Then be placed in Muffle furnace and calcine, calcination time is 2.5 hours, and calcining heat is 350 DEG C, and heating rate is 10 DEG C/min.Naturally cobalt acid nickel multi-pore micron crystal whisker array/nickel foam combination electrode material is namely obtained after cooling.
In mass percentage, product purity is not less than 99.96%, impurity content: carbon is less than 0.02%; Nitrogen is less than 0.02%.Using prepared cobalt acid nickel multi-pore micron crystal whisker array/nickel foam combination electrode material directly as work electrode.Under three-electrode system, test constant current charge-discharge performance, when current density is 5A/g, its ratio capacitance value is up to 619F/g.The ratio capacitance value after 3000 times that circulates only has decayed 3.6%.
Embodiment 3.
The nickel foam of cleaning is immersed in the oxalic acid aqueous solution of 0.1mol/L, it is 25 DEG C in temperature, mixing speed is under the condition of 100 revs/min, the mixed aqueous solution of nickel nitrate and cobalt nitrate is dripped in oxalic acid aqueous solution, wherein nickel nitrate molar concentration is 0.5mol/L, wherein cobalt nitrate molar concentration is 1.0mol/L, and rate of addition is 60 droplets/minute, and the mol ratio of final nickel nitrate and oxalic acid is 1:6.The stirring reaction time is 30 minutes.After reaction terminates, after nickel foam is taken out washing, put into baking oven, programmed rate 5 DEG C/min, drying 2 hours under 100 DEG C of conditions.Then be placed in Muffle furnace and calcine, calcination time is 2.5 hours, and calcining heat is 350 DEG C, and heating rate is 10 DEG C/min.Naturally cobalt acid nickel multi-pore micron crystal whisker array/nickel foam combination electrode material is namely obtained after cooling.
In mass percentage, product purity is not less than 99.96%, impurity content: carbon is less than 0.02%; Nitrogen is less than 0.02%.Using prepared cobalt acid nickel multi-pore micron crystal whisker array/nickel foam combination electrode material directly as work electrode.Under three-electrode system, test constant current charge-discharge performance, when current density is 5A/g, its ratio capacitance value is up to 655F/g.The ratio capacitance value after 3000 times that circulates only has decayed 3.7%.
Embodiment 4.
The nickel foam of cleaning is immersed in the oxalic acid aqueous solution of 1.5mol/L, it is 25 DEG C in temperature, mixing speed is under the condition of 100 revs/min, the mixed aqueous solution of nickel chloride and cobalt chloride is dripped in oxalic acid aqueous solution, wherein nickel chloride molar concentration is 0.25mol/L, wherein cobalt chloride molar concentration is 0.5mol/L, and rate of addition is 60 droplets/minute, and the mol ratio of final nickel chloride and oxalic acid is 1:30.The stirring reaction time is 15 minutes.After reaction terminates, after nickel foam is taken out washing, put into baking oven, programmed rate 5 DEG C/min, drying 2 hours under 100 DEG C of conditions.Then be placed in Muffle furnace and calcine, calcination time is 2.5 hours, and calcining heat is 350 DEG C, and heating rate is 10 DEG C/min.Naturally cobalt acid nickel multi-pore micron crystal whisker array/nickel foam combination electrode material is namely obtained after cooling.
In mass percentage, product purity is not less than 99.96%, impurity content: carbon is less than 0.02%; Chlorine is less than 0.02%.Using prepared cobalt acid nickel multi-pore micron crystal whisker array/nickel foam combination electrode material directly as work electrode.Under three-electrode system, test constant current charge-discharge performance, when current density is 5A/g, its ratio capacitance value is up to 579F/g.The ratio capacitance value after 3000 times that circulates only has decayed 3.8%.
Embodiment 5.
The nickel foam of cleaning is immersed in the oxalic acid aqueous solution of 0.5mol/L, it is 25 DEG C in temperature, mixing speed is under the condition of 100 revs/min, the mixed aqueous solution of nickel chloride and cobalt chloride is dripped in oxalic acid aqueous solution, wherein nickel chloride molar concentration is 0.05mol/L, wherein cobalt chloride molar concentration is 0.1mol/L, and rate of addition is 180 droplets/minute, and the mol ratio of final nickel chloride and oxalic acid is 1:6.The stirring reaction time is 30 minutes.After reaction terminates, after nickel foam is taken out washing, put into baking oven, programmed rate 5 DEG C/min, drying 2 hours under 100 DEG C of conditions.Then be placed in Muffle furnace and calcine, calcination time is 2.5 hours, and calcining heat is 350 DEG C, and heating rate is 10 DEG C/min.Naturally cobalt acid nickel multi-pore micron crystal whisker array/nickel foam combination electrode material is namely obtained after cooling.
In mass percentage, product purity is not less than 99.95%, impurity content: carbon is less than 0.02%; Chlorine is less than 0.03%.Using prepared cobalt acid nickel multi-pore micron crystal whisker array/nickel foam combination electrode material directly as work electrode.Under three-electrode system, test constant current charge-discharge performance, when current density is 5A/g, its ratio capacitance value is up to 512F/g.The ratio capacitance value after 3000 times that circulates only has decayed 3.6%.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. the preparation method of cobalt acid nickel multi-pore micron band/nickel foam combination electrode material, it is characterized in that: the nickel foam of cleaning is immersed in oxalic acid aqueous solution, in room temperature and stir condition under, in above-mentioned solution, drip soluble nickel salt and soluble cobalt mixed aqueous solution; Stirring reaction, until nickel foam surface-borne goes out micrometer structure presoma, takes out nickel foam, namely obtains object product after cleaning successively, drying and calcining.
2. the preparation method of a kind of cobalt acid nickel multi-pore micron band/nickel foam combination electrode material according to claim 1, is characterized in that: the molar concentration of described oxalic acid aqueous solution is 0.1 ~ 2.0mol/L; Described room temperature is at 20 ~ 30 DEG C; Described mixing speed remains on 100 ~ 150 revs/min; The speed of described dropping solution is 60 ~ 180 droplets/minute; The described stirring reaction time is 10 ~ 30 minutes.
3. the preparation method of a kind of cobalt acid nickel multi-pore micron band/nickel foam combination electrode material according to claim 2, is characterized in that: described soluble nickel salt is one or its mixture of nickel nitrate or nickel chloride, and its molar concentration is 0.05 ~ 0.5mol/L; Described soluble cobalt is one or its mixture of cobalt nitrate or cobalt chloride, and its molar concentration is 0.1 ~ 1.0mol/L; The mol ratio of nickel salt and cobalt salt is 1:2; The mol ratio of nickel salt and oxalic acid is 1:6 ~ 60.
4. the preparation method of a kind of cobalt acid nickel multi-pore micron band/nickel foam combination electrode material according to claim 3, it is characterized in that: described drying time is 1 ~ 3 hour, baking temperature is 60 ~ 120 DEG C, and heating rate is 2 ~ 10 DEG C/min.
5. the preparation method of a kind of cobalt acid nickel multi-pore micron band/nickel foam combination electrode material according to claim 4, it is characterized in that: described calcination time is 2 ~ 5 hours, calcining heat is 300 ~ 450 DEG C, and heating rate is 2 ~ 20 DEG C/min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510848187.5A CN105470002A (en) | 2015-11-27 | 2015-11-27 | Preparation method of nickel cobaltite porous micron belt/foamed nickel composite electrode material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510848187.5A CN105470002A (en) | 2015-11-27 | 2015-11-27 | Preparation method of nickel cobaltite porous micron belt/foamed nickel composite electrode material |
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| CN105470002A true CN105470002A (en) | 2016-04-06 |
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| CN106098414A (en) * | 2016-07-27 | 2016-11-09 | 河南师范大学 | The method of one step hydro thermal method synthesizing graphite alkene nickel hydroxide complex electrode of super capacitor |
| CN106129401A (en) * | 2016-06-29 | 2016-11-16 | 北京化工大学 | A kind of foamed nickel supported high surface roughness cobalt acid nickel nm wall and preparation method thereof |
| CN109599564A (en) * | 2018-11-27 | 2019-04-09 | 东华大学 | Cobalt acid nickel array self-supporting large area air electrode and its preparation and application |
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| CN109599564B (en) * | 2018-11-27 | 2022-09-06 | 东华大学 | Nickel cobaltate array self-supporting large-area air electrode and preparation and application thereof |
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